NO172806B - WATER-CURRENT POLYMER PREPARATION, PREPARATION AND APPLICATION OF THEREOF - Google Patents

Description

The invention relates to water-hardening polymer preparations for construction materials, especially for medical support bandages or technical devices which, as additives, contain polyetherpolysiloxane-polyurethanes, a method for their production and their use.

The present invention also relates to a method for producing such water-hardening polymer preparations and the invention also relates to the use of these preparations in the production of medical support bandages and in the production of technical construction materials.

The construction materials usually consist of a carrier layer that is coated and/or impregnated with a water-hardening polymer preparation.

In general, the construction materials according to the invention can be used for stiffening, shaping and sealing in the medical and technical areas. In the medical field, they are preferably used as a plaster substitute.

However, the construction materials according to the invention can also be used for the manufacture of containers, filters of pipes for connecting construction elements for the manufacture of decorative or artistic articles for stiffening purposes or as filling or sealing materials for joints and cavities.

Construction materials consisting of a flexible carrier coated and/or impregnated with a water-curing reactive resin are already known. For example, reference should be made to DE-Å 23 57 931, which refers to construction materials of flexible carriers such as wood, woven fabric or fleece, which are coated or impregnated with water-hardening reactive resins such as isocyanates or prepolymers modified with isocyanate groups.

The water-curing polymer preparations known from DE-Å 23 57 931 and the later developments have the disadvantage that they can only be easily modulated, especially during the curing phase when they develop a strong stickiness.

According to EP-A 02 21 669, this problem is attempted to be solved by adding lubricants. The plate structures mentioned in EP-A 02 31 669, for example orthopedic bandages, consisting of a carrier coated with a water-hardening polymer preparation, which is largely coated with a lubricant on the surface. By lubricants are meant compounds with hydrophilic groups that are covalently bound to the polymer, or additives that are incompatible with the polymer. The amount of lubricant is chosen so high that they cause a kinetic coefficient of friction of the coated raft structure of less than 1.2. The raft structures treated in this way have a slight stickiness. Polysiloxanes are also used as incompatible, non-miscible additives (page 8, line 28 to page 10, line 8).

In the case of the known materials, for a clear reduction of the kinetic coefficient of friction (for example below 1.2) it is necessary that a lubricant is present that has hydrophilic groups that are bound to polymers and/or that an additive is present that for example the aforementioned polysiloxanes which are not miscible with the polymer preparation, i.e. must be applied separately.

The present invention aims to improve the known technique and thus relates to a water-curing polymer preparation for construction materials containing as an additive polyetherpolysiloxane-polyurethanes with the formula

there

R<1> means lower alkyl,

m means the average number of the siloxane group in the range 5 to 25,

and this water-curing polymer preparation is characterized by the fact that

R means the rest

there

X means a lower alkylene residue,

Y means an aliphatic, cycloaliphatic, aromatic or

araliphatic residue,

Z means a polyether residue with ethylene oxide and/or propylene oxide groups, the average number of ethylene oxide and/or propylene oxide groups being in the range from 5 to

150, and

R<2> means lower alkyl, as

Y may be further substituted with

Z and R<2> have the above meaning.

The additives are compatible with polymer formulations and mix completely with them. They show excellent storage stability, and also do not separate after more than 12 months of storage.

The advantage of the systems described lies in the fact that they can already be mixed with the reactive resins during production, which saves a processing step compared to known materials.

The preparations can be easily modulated during the curing time, however, during the processing phase they are not as smooth as the compounds according to EP-A 221 669, where the lubricant is applied as a separate layer. The preparations according to the invention develop a modulability only after moistening with water, which enables convenient processing. The kinetic coefficient of friction is then likewise below 1.2, which is reflected in the low stickiness.

Within the scope of the present invention, the substituents of the polyetherpolysiloxane polyurethanes can generally have the following meaning: Lower alkyl can generally mean a straight or branched C^_^ hydrocarbon residue. For example, mention should be made of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl. Methyl and ethyl are preferred. Methyl is particularly preferred.

The lower alkyl can generally mean a 2-valent straight or branched C^_^ hydrocarbon residue. Examples are methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, iso-pentylene, hexylene and isohexylene. Methylene, ethylene and propylene are preferred.

An aliphatic residue can generally mean a straight or branched aliphatic C2-18-' preferably C^_^g hydrocarbon residue. Examples are the following residues:

Preferred is -(Cltø^-.

A cycloaliphatic residue can generally be a cycloaliphatic<C>4-15-'f°r"tr:i-imsvls a C5_1Q-hydrocarbon residue. Examples are the following cycloaliphatic hydrocarbon residues:

An aromatic residue may generally be an aromatic C 15 - preferably a C 15 -hydrocarbon residue. Aromatic residues include phenyl, naphthyl and biphenyl, phenyl being preferred.

An araliphatic residue can generally be an araliphatic Cg_^5-, preferably a Cg_^3-hydrocarbon residue. As araliphatic residues are mentioned benzyl,

Preferred are:

The mentioned aliphatic, cycloaliphatic, aromatic and araliphatic residues (Y) may optionally be substituted with further, preferably with two and preferably with a further substituent with the formula

For Y, residues deriving from the following low molecular weight polyisocyanates must be mentioned in detail as examples: Suitable such low molecular weight polyisocyanates are, for example, hexamethylene diisocyanate, 1,12-dodecane isocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1, 4-diisocyanate as well as arbitrary mixtures of these isomers, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexa-hydrotoluenediisocyanate as well as desirable mixtures of these isomers, hexahydro-1,3 - and/or -1,4-phenylenediisocyanate, perhydro-2,4'- and/or -4,4'-diphenylmethane isocyanate, 1,3- and 1,4- phenylenediisocyanate, 2,4- and 2,6-toluylene diisocyanate as well as desirable mixtures of these isomers, diphenylmethane-2,4'- and/or -4,4'-isocyanate, naphthylene-1,5-diisocyanate, triphenyl-methane-4,4'-4"-triisocyanate or polyphenylpolymethylene polyisocyanates as formed by aniline formaldehyde condensation and subsequent phosgenation.

Suitable higher molecular polyisocyanates are modification products of such simple polyisocyanates, i.e. polyisocyanates with, for example, isocyanurate, carbodiimide, allophanate, biuret or uretdione structural units, as can be produced by methods known per se according to the art state, from the example mentioned simple polyisocyanates of the above general formula.

According to the invention, particularly preferred polyisocyanate components are the technical polyisocyanates common in polyurethane chemistry, i.e. hexamethylene diisocyanate 2,4- and 2,6-toluene diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, abbreviated IPDI), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diiso-cycanatodiphenylmethane, their mixtures with the corresponding 2,4'- and 2,2'-isomers, polyisocyanate mixtures of the diphenylmethane series, as they can be prepared by phosgenation of aniline/formaldehyde condensates in a manner known per se, and the biuret or isocyanurate group-containing modification products of these technical polyisocyanates as well as desirable mixtures of such polyisocyanates. Isocyanates with aromatically bound NCO groups are preferred according to the invention. A particularly preferred polyisocyanate component according to the invention is 2,4- and 2,6-toluenediisocyanate and/or mixtures of the two isomers.

The polyether residue usually consists (largely) of ethylene oxide and/or propylene oxide groups. Preferably, it consists of ethylene oxide and propylene oxide groups. The average total number of ethylene oxide and propylene oxide groups is usually in the range from 5 to 150, preferably from 10 to 100. For the preferred case that the polyether residue consists of ethylene oxide and propylene oxide groups, the weight ratio of ethylene oxide:propylene oxide is usually 10:90 to 80:20 , preferably 20:80 to 75:25.

The ethylene oxide and propylene oxide groups can be arranged statistically alternating or in blocks. A statistical distribution is preferred.

Preferably, the water-curing polymer preparations according to the invention can contain as additives polyetherpolysiloxane polyurethanes of formula I, in which

Ri means methyl or ethyl,

m means the average number of siloxane groups in the range from 5 to 25,

R means the rest

in which

X means alkylene (C1 to C4),

Y means an aliphatic C2_lg hydrocarbon residue,

a cycloaliphatic C4_15 hydrocarbon residue,

an aromatic C^_^5-hydrocarbon residue, or

an araliphatic C 8 -^5 hydrocarbon residue.

Z means a polyether residue with ethylene oxide and propylene oxide groups, the average number of ethylene oxide and

propylene oxide groups are in the range from 10-100 and

R<2>means alkyl (C1 to C4),

wherein the weight ratio of ethylene oxide:propylene oxide groups amounts to 10:90 to 80:20, and wherein

Y may be substituted with one or two more

in which

Z and R<2> have the meaning given above.

Particularly preferably, the water-curing polymer preparations according to the invention may contain as additives polyether-polysiloxane-polyurethanes of formula I, in which R<1> means methyl or ethyl,

m means the average numbers of siloxane groups in the range from 5

to 25,

R means the rest

in which

X means alkylene {C1 to C4),

Y means an aliphatic C^_1Q hydrocarbon residue,

a C5_1Q cycloaliphatic hydrocarbon residue,

an aromatic C6_13~hydrocarbon residue, or

an araliphatic Cg_13 hydrocarbon residue,

Z means a polyether residue with ethylene oxide and propylene oxide groups, the average number of ethylene oxide and propylene oxide groups being in the range from 10 to 100, and

R<2>means alkyl (C1 to C4),

wherein the weight ratio between ethylene oxide and propylene oxide groups amounts to 10:90 to 80:20, and wherein

Y may be substituted with a further one

in which

Z and R<2> have the meaning given above.

The group of polyetherpolysiloxane polyurethanes used as additives is in, and known per se (DE-A 25 58 523, US-PS 4 096 162), they are used as stabilizers for polyurethane foam.

The polyetherpolysiloxane polyurethanes can be produced by reacting the isocyanate OCN-Y-NCO with a monohydroxy functional polyether HO-Z-R<2> and the reaction product OCN-Y-NE-CO-0-Z-R<2> then reacting with a bishydroxyalkyldialkylpolysiloxane

while

X, Y, Z, R<*>, R<2> and m have the meaning given above.

The water-curing polymer preparations according to the invention usually contain 0.1 to 10% by weight, preferably 0.1 to 8% by weight, of polyetherpolysiloxane-polyurethanes, calculated on the polymer resin, the kinetic coefficient of friction being 0.5 or more, less than that without the amount of corresponding additives.

Of course, it is possible that the water-curing polymer preparations according to the invention contain more than the aforementioned polyetherpolysiloxane polyurethanes as additives.

Water-curing polymer preparations are preferably resins based on polyurethane or polyvinyl resin.

Particularly preferred are polyisocyanates or prepolymers with free isocyanate groups (polyurethanes).

As water-curing polyisocyanates and polyurethanes respectively, all organic polyisocyanates known per se are mentioned, i.e. desirable compounds or mixtures of compounds which have at least two organically bound isocyanate groups per molecule. This also includes low-molecular polyisocyanates with a molecular weight below 400, as well as modification products of such low-molecular polyisocyanates with a molecular weight, calculable from functionalities and the content of functional groups, for example from 400 to 10,000, preferably 600 to 8,000, and especially 800 to 5000. Suitable lower molecular weight polyisocyanates are, for example, those with formula

in which

n means 2-4, preferably 2-3, and

Q means an aliphatic C2- ±8~' for°r"tr:i-nns a C6_io~nvdro_

carbon residue,

a cycloaliphatic C£— i§~ > preferably a Cg_1Q hydrocarbon residue,

an aromatic C£,_i5~»preferably a C^_13~ hydrocarbon residue, or

an araliphatic cg_^5_, preferably a Cg_13 hydrocarbon residue.

Suitable such low molecular weight polyisocyanates are, for example, hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate as well as desirable mixtures of these isomers, l-isocyanato-3,3, 5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexa-hydrotoluenediisocyanate and desirable mixtures of these isomers, hexahydro-1,3- and/or 1,4-phenylenediisocyanate, perhydro-2,4' - and/or -4,4'-diphenylmethane diisocyanate, 1,3-and 1,4-phenylenediisocyanate, 2,4- and 2,6-toluylene diisocyanate as desirable mixtures of these isomers, diphenylmethane-2,4'-and/or -4,4'-isocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4',4"-triisocyanate or polyphenylpolymethylene polyisocyanates as obtained by aniline formaldehyde condensation and subsequent phosgenation.

Suitable higher molecular polyisocyanates are modification products of such simple polyisocyanates, i.e. polyisocyanates with, for example, isocyanurate, carbodiimide, allophanate, biuret and uretdione structural units, so that they can be produced according to per se known methods in accordance with the art stand from the simple polyisocyanates mentioned as examples with the general formula mentioned above. Among the higher molecular weight modified polyisocyanates, the prepolymers known from polyurethane chemistry are particularly of interest, with end-positioned isocyanate groups of the molecular weight range 400 to 10,000, preferably 600 to 8,000, and especially 800 to 5,000. These compounds are produced in a manner known per se, by reaction of excess amounts of simple polyisocyanates of the type mentioned as an example with organic compounds with at least two groups capable of reacting with isocyanate groups, especially organic polyhydroxyl compounds. Suitable such polyhydroxyl compounds are simple polyhydric alcohols such as ethylene glycol, trimethylol-propane, propanediol-1,2- or butanediol-1,2-, as well as higher molecular polyether polyols and/or polyester polyols of the type known per se from polyurethane chemistry, with molecular weights from 600 to 8000, preferably 800 to 4000, which have at least two usually 2-8, however preferably 2-4 primary and/or secondary hydroxyl groups. Of course, such NCO prepolymers can also be used, for example formed from lower molecular weight polyisocyanates of the type mentioned for example, and less preferred compounds with groups capable of reacting with isocyanate groups such as for example polythioether polyols, polyacetals containing hydroxyl groups, polyhydroxy polycarbonates, polyester amides containing hydroxyl groups or copolymers containing hydroxyl groups of olefinically unsaturated compounds. For the production of the NCO prepolymers suitable compounds with groups reactive towards isocyanate groups, especially hydroxyl groups, are for example those in US-PS 4 218 543 column 7, line 29 to column 9 line 25, for example the compounds mentioned are particularly suitable. In the preparation of the NCO prepolymers, these compounds with groups capable of reacting with isocyanate groups are reacted with simple polyisocyanates of the type mentioned above as an example while maintaining an NCO:OH equivalent ratio of over 1. The NCO prepolymers usually have an NCO content of 2 .5 to 30, preferably 6 to 25 weight-Sé. It already follows from this that within the scope of the present invention, "NCO prepolymers" or "prepolymers with end-placed isocyanate groups" are understood to mean both the reaction products as such, as well as their mixtures with excess amounts of unreacted starting polyisocyanates, which often also referred to as "semiprepolymer".

According to the invention, particularly preferred polyisocyanate components are the common technical polyisocyanates in polyurethane chemistry, i.e. hexamethylene diisocyanate 1-isocyanato-3,3,5-trime ty 1-5-isocyanate ome ty 1-cyclohexane (isophorone diisocyanate, abbreviated IPDI), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanato-diphenylmethane, their mixtures with the corresponding 2,4'- and 2,2'-isomers, polyisocyanate mixtures of the diphenylmethane series, as they can be prepared by phosgenation of aniline/formaldehyde condensates in a manner known per se, the biuret or isocyanate group-containing modification products of these technical polyisocyanates and especially NCO prepolymers of the mentioned type based on these technical polyisocyanates on the one hand, and the simple polyols mentioned as examples and/or polyether polyols and/or polyester polyols on the other hand, as well as desirable mixtures of such polyisocyanates. Isocyanates with aromatically bound NCO groups are preferred according to the invention. A particularly preferred polyisocyanate component according to the invention is partially carbodiimidized diisocyanatodiphenylmethane, which due to the addition of monomeric diisocyanate to the carbondiimide structure also has uretonimine groups.

The water-curing polyurethanes can contain per se known catalysts. In particular, these can be tertiary amines that catalyze the isocyanate/water reaction and not a self-reaction (trimerization, allophanatization) (DE-A 23 57 931). As examples, mention should be made of tertiary amine-containing polyethers (DE-A 26 51 089), low molecular weight tertiary amines which

ethyl ether or bis-(2,6-dimethylmorpholino)-diethyl ether (W0 86/01397). Catalyst content, calculated on the tertiary nitrogen, is usually 0.05 to 0.5 wt-#, calculated on the polymer resin.

Water-curing polyvinyl resins can, for example, be vinyl compounds consisting of a hydrophilic prepolymer with more than 1 polymerizable vinyl group, in which a solid insoluble vinyl ethoxy catalyst is embedded, one component of which is encapsulated by a water-soluble or water-permeable casing. Such a redox catalyst is, for example, sodium hydrogen sulphite/copper (II) sulphate, where, for example, copper sulphates are encapsulated with poly-2-hydroxyethyl methyl acrylate.

Polyvinyl resins are described, for example, in EP-A 01 36 021.

The water-hardening polymer preparations may contain per se known additives such as flow aids, thixotroping agents, defoamers and other known lubricants.

Furthermore, the plastic resins can be colored or, if desired, contain UV stabilizers.

Examples of additives include: polydimethylsiloxanes, calcium silicates of the Aerosil type, polywax (polyethylene glycols), UV stabilizers of the ionol type (DE-A 29 21 163), color pigments such as carbon black, iron oxides, titanium dioxide, or phthalocyanines.

Additives particularly suitable for polyurethane prepolymers are discussed in "Kunststoff-Handbuch", volume 7, polyurethanes, pages 100-109 (1983). They are usually added in an amount of 0.5 to 5%, (calculated on the resin)..

As carrier materials, massive or porous foils, or also foams of natural or synthetic materials, (for example polyurethane), primarily air-permeable flexible raft structures on a textile basis, preferably with a basis weight of 20 to 1000 g/m<2>, are taken into consideration. especially from 30 to 500 g/m<2>. As examples of fleet structures, the following should be mentioned:

Carrier material:

1. Textiles, weaves, works or knitting, with a basis weight of 20-400 g/m<2>, preferably 40-250 g/m<2> with 25-100 rows of stitches per 10 cm, preferably 30 to 75 rows of stitches per 10 cm, and 30-90 double crochets per 10 cm, preferably 40 to 80 stitches per 10 cm. The textile weaving, working or knitting can be made from desirable natural or synthetic yarns. Preferably yarn is used which consists of cotton, polyester, polyacrylate, polyamide or elastane fibers or mixtures thereof. Particularly preferred are textile carriers of the above-mentioned yarns which have an extension in the longitudinal direction from 10-100$, and/or in the transverse direction from 20 to 30056. 2. Glass fiber woven, knitted or knitted fabrics of a basis weight of 60-500 g / m2, preferably 100-400 g/m<2>, made of glass fiber yarn with an E-modulus 7000 to 9000, (daN/mm<2>), and a thread drop of 3-10, preferably 5-7 in the longitudinal direction, and with a thread count of 3-10, preferably 4-6 in the transverse direction per cm. fiberglass fabric which, with a special type of heat treatment, has a longitudinal elasticity of 10-30$, is preferred. The works can be either glued or unglued. 3.

Non-bonded or bonded or needled fleece based on inorganic, and preferably organic fibers of a basis weight of 30-400 g/m<2>, preferably 50-200 g/m<2>.

For the production of construction materials as described in the form of bowls or rails, flour in basis weights up to 1000 g/m<2.>According to the invention suitable carrier materials are also mentioned, for example, in US-PS 4 134 397, US-PS 3 686,725, US-PS 3,882,857, DE-A 3,211,634 and EP-A 61,642.

With the construction materials, the carrier material is coated and/or impregnated with an amount of 25-80 weight-$, preferably 30-75 weight-$ of water-hardening polymer preparation, calculated on the total material.

As mentioned above, the invention also relates to a method for producing the above-described water-curing polymer preparations and this method is characterized by mixing a water-curing reactive resin with a polyetherpolysiloxane-polyurethane additive according to claim 1 while adding catalysts and further auxiliaries and additives, after which the mixture is distributed homogeneously over the surface of a carrier.

Finally, as mentioned at the outset, the invention relates to the use of the above-described water-hardening polymer preparations for construction materials, containing as an additive polyether-polysiloxane-polyurethanes as described above, in the production of medical support bandages and technical construction materials.

In the method according to the invention, one works under the exclusion of moisture. Work is preferably done at a relative humidity of less than 2% (at 21°C), particularly preferred at less than 1% (at 21°C).

For coating or impregnation, the polymer preparation can be dissolved in an inert solvent, which, after the coating process, is again removed.

Inert solvents can be, for example, chlorinated hydrocarbons, such as methylene chloride, trichloroethane, or chloroform, ketones such as acetone and methyl ethyl ketone, esters such as acetic acid ethyl esters and butyl acetate, aromatics such as toluene, xylene or similar derivatized types, which do not have Zerewitinoff-active hydrogen.

For example, the construction materials can be produced as follows:

Usually, the carrier material is allowed to run over a roller, and it is impregnated with the polymer preparation, possibly in a solvent. Immediately after the coating or impregnation, the material is rolled up to the desired length (usually 2-11 m) on suitable spools, and sealed in an airtight and waterproof foil (for example made of plastic-aluminium laminate), or other completely sealed containers, as is mentioned in DE-A 23 57 931, DE-A 26 51 089 and DE-A 30 33 569.

Immediately before use, the material is removed from the packaging, wrapped or otherwise placed around the object in question.

For curing, the preparation according to the invention is brought into contact with water, possibly also only with atmospheric humidity.

The curing time is usually short (3-15 minutes). During this time, the preparation according to the invention is surprisingly well modulated. They hardly show stickiness, their coefficient of kinetic friction is usually below 1.0.

The polymer modification according to the invention, which significantly facilitates the processing of the coated carrier material, does not affect the properties of the cured construction materials with regard to hardness, fracture expansion, layer composition.

Example 1

Preparation of reactive resin additive.

94.2 g of toluylene 2,4- and 2,6-diisocyanate mixture in an isomer ratio of 80:20 is added to an apparatus consisting of a three-necked flask with stirrer, dropping funnel and reflux condenser in 250 ml of absolute methylene chloride.

To this, 1200 g of a monofunctional polyether are dripped, started on n-butanol with a mixture block of 15% propylene oxide and 65% ethylene oxide, and a final block of 20% ethylene oxide,

(average molecular weight: 2440 g/mol), slowly under reflux of the mixture. After the addition is complete, it is heated for another 1/2 hour under reflux.

153 g of a bishydroxymethyl-functional polydimethylsiloxane with an average molecular weight of 566 g/mol are then added, and the reaction mixture is heated for a further 2 hours under reflux. For processing, the overall reaction mixture is freed on a rotary evaporator for solvent and can be used as an additive.

Example 2

Production of a water-curing reactive resin. (using the additive from example 1.

6.48 kg of isocyanate (bis-(4-isocyanatophenyl)-methane containing carbodiimidized parts [NCO content = 29$]) is added to a 10 liter sulphurisation vessel with stainless steel anchor stirrers. 7.8 g of a polydimethylsiloxane with n = 30,000 mPas and 4.9 g of benzoyl chloride are then added, as well as, then, 1.932 kg of a polyether produced by propoxylation of propylene glycol (OH number = 112 mg K0H/g), 1.29 kg of a polyether produced by propylation of propylene glycol (OH number = 250 mg K0H/g), and 190 g of dimorpholindiethyl ether. After 30 minutes the reaction temperature reaches 45°C, after 1 hour a temperature maximum of 56°C has been reached, and the isocyanate content amounts to 14.2$. 500 g of the additive mentioned in example 1 is then added to the reaction mixture, and the whole is stirred until homogeneity. The isocyanate content at the end is 13.2%, the viscosity is 19,950 mPa.s.

Example 3

Production of a water-hardening reactive resin (see example without additive).

6.48 kg of isocyanate (bis-(4-isocyanatophenyl)-urethane, which contains carbodiimidized parts [NCO content = 29$]) is added to an apparatus analogous to example 2. Then 7.8 g of a polydimethylsiloxane with n = 30,000 mPa.s, and 4.9 g of benzoyl chloride are added as well as, then, 1.93 kg of a polyether produced by means of propoxylation of propylene glycol (OH number = 112 mg KOH /g), 1.29 g of a by propoxylation of glycerol-formulated polyether (OH number = 250 mg KOH/g), and 190 g of dimorpholinodiethyl ether. After 30 minutes the reaction temperature reaches 42°C, after 1 hour a temperature maximum of 48°C has been reached, and the cyanate content amounts to 13.6$. The viscosity is at 17,800 mPa.s.

Example 4

Preparation of a water-curing reactive resin (using the additive from example 1).

6.5 kg of isocyanate (bis-(4-isocyanatophenyl)-methane, which contains carbodiimidized parts, [NCO content = 29$]) is added to a 10 liter sulfurization vessel with stainless steel anchor stirrers, and preheated to approx. 50°C. To this is added 150 g of a UV stabilizer (a cyanoalkylindole derivative) and it is stirred until the total solid has dissolved. After cooling to room temperature, 3.5 kg of propoxylated triethanolamine (OH number = 150 mg KOH/g) are added within 20 minutes. After a short temperature increase to 55°C after 55 minutes, the temperature drops again and the isocyanate content reaches 13.4$ after 2 hours. After adding 534.2 g of the additive mentioned in example 1, the reaction mixture is stirred until homogeneity, its viscosity is at 19,056 mPa.s (25°C).

Example 5

Production of a water-hardening reactive resin (see example without additive).

6.5 kg of isocyanate (bis)-4-isocyanatophenyl)-methane containing carbodiimidized parts [NCO content = 29$] ) are added to a 10-litre sulphurisation vessel with stainless steel anchor stirrers and the whole is preheated to approx. 50°C. To this is added 150 g of a TJV stabilizer (a cyanoalkylindole derivative) and it is stirred until the total solid has dissolved. After cooling to room temperature, 3.5 kg of propoxylated triethanolamine (OH number = 150 mg K0H/g) is added within 10 minutes. After a short temperature increase to 55°C, 55 minutes, the temperature drops again, and the isocyanate content reaches 13.4$ after 2 hours. The isocyanate content of the finished prepolymer amounts to 12.7%, the viscosity is at 14,640 mPa.s (25°C).

Example 6

Production of sample bandages. ier with the reactive resins According to examples 2-5.

6a) A fiberglass mixture (width 10.0 cm, m<2->weight approx. 290

g/m<2>), which in the longitudinal direction has an expansion of approx. 65$

(a detailed description of this timber can be found in US-PS 4 609 578), is coated with 80 wt.-$ (referred to timber), of the resin according to example 2. The coating takes place in a

atmosphere whose relative humidity is characterized by a water dew point of less than -20°C. The resin is applied homogeneously to the timber over a suitable roller impregnation agent. A suitable apparatus is described in detail in US-PS 4,427,002. After coating, 3.66 m of this tape is wound

on a plastic coil of 1 cm diameter, and sealed in a foil impermeable to water vapour.

6b) Analogously to example 6a), fiberglass timber is coated and prepackaged with 80 weight-$ (referred to timber) of the resin from example 3.

6c) Analogously to example 6a), the glass fiber timber is coated and prepackaged with 70 weight-$ (calculated on the timber) of the resin from example 4.

6d) Analogously to example 6a), the glass-fibre wood is coated and prepackaged with 70 weight-$ (calculated on the wood) of the resin from example 5.

6e) Analogous example 6a) becomes a polyester work (width 10.0

cm, weight per square meter 118 g/m<2>), which in the longitudinal direction has an expansion of approx. 55$ and in the transverse direction an extension of approx. 90$, and which in the stitch bar has a polyfelt textured polyester filament yarn (167 dtex, f. 30x1), and in the stitch row has a polyfelt high tenacity polyester filament yarn (550 dtex, f. 96, normal shrink), coated and

packaged with 150 weight # (calculated on the wood) of the resin from example 2.

6f) Analogously to example 6a), the polyester timber mentioned in example 6e) is coated and prepackaged with 150 weight-$ (calculated on the timber) of the resin from example 2.

Example 7

Determination of the kinetic f riks. ion coefficient of the coated carrier materials 6a)- 6f).

In a completely analogous manner to EP 211 669, the kinetic coefficient of friction was determined corresponding to the ASTM D-1894 test with an "ApReibungs-koeffizienttron Corp." (Instron Coefficient of Friction Figure; Catalog N, 2810-005) and the stainless steel conductor mentioned in EP-A 211 669, page 13, determined the kinetic coefficient of friction.

The test bandage was taken out of the packaging after 1 month and prepared and measured as described in EP-A 221 669, pages 14, 15. The force measurement took place with a ZWICK Universal Testing Machine type 1484.

Claims (7)

1. Water-curing polymer preparation for construction materials containing as an additive polyetherpolysiloxane-polyurethanes with formula there R<1> means lower alkyl, m means the average number of the siloxane group in the range 5 to 25, characterized by R means the rest there X means a lower alkylene residue, Y means an aliphatic, cycloaliphatic, aromatic or arali phatic residue, Z means a polyether residue with ethylene oxide and/or propylene oxide groups, the average number of ethylene oxide and/or propylene oxide groups being in the range from 5 to 150, and R<2> means lower alkyl, as Y may be further substituted with Z and R<2> have the above meaning. 2. Polymer preparation according to claim 1, characterized by X means C1_4-alkylene, Y represents an aliphatic C2_i8~ny^rocar^onres"t» a cycloali phatic C4_25~ hydrocarbon residue, an aromatic C^_^5 hydrocarbon residue or an araliphatic C8_i5 hydrocarbon residue, Z means a polyether residue with ethylene oxide and propylene oxide groups, the average number of ethylene oxide and propylene oxide groups being in the range 10 to 100, and R<2> means C1_4-alkyl, wherein the weight ratio between ethylene oxide and propylene oxide groups amounts to 10:90$ to 80:20$, and wherein Y may be substituted by one or two more there Z and R<2> have the above meanings. 3. Polymer preparations according to claims 1 and 2, characterized by X is C 1-4 alkylene, Y means an aliphatic C 2 -hydrocarbon residue, a cyclo aliphatic C5_iø hydrocarbon residue f an aromatic cb-13~ hydrocarbon residue or an araliphatic Cg_13 hydrocarbon residue, Z means a polyether residue with ethylene oxide and propylene oxide groups, the average number of ethylene oxide and propylene oxide groups being in the range from 10 to 100, and R<2>means C1_4-alkyl, wherein the weight ratio between ethylene oxide and propylene oxide groups amounts to 10:90$ to 80:20$, and in that Y may be substituted with a further one there Z and R<2> have the above meaning. 4. Water-curing polymer preparations according to claims 1-3, containing 0.1 to 10% by weight of polyetherpolysiloxane-polyurethanes referred to water-curing polymer. 5. Process for the production of water-curing polymer preparations for construction materials, characterized in that a water-curing reactive resin is mixed with a polyetherpolysiloxane-polyurethane additive according to claim 1 while adding catalysts and further auxiliaries and additives, after which the mixture is homogeneously distributed over the surface of a carrier. 6. Use of water-hardening polymer preparations for construction materials, containing as additive polyether-polysiloxane-polyurethanes according to claims 1 to 4, in the manufacture of medical support bandages. 7. Use of water-hardening polymer preparations for construction materials, containing as an additive polyether-polysiloxane-polyurethanes according to claims 1 to 4, in the production of technical construction materials.